JPH07187930A - Antimicrobial agent - Google Patents
Antimicrobial agentInfo
- Publication number
- JPH07187930A JPH07187930A JP32724593A JP32724593A JPH07187930A JP H07187930 A JPH07187930 A JP H07187930A JP 32724593 A JP32724593 A JP 32724593A JP 32724593 A JP32724593 A JP 32724593A JP H07187930 A JPH07187930 A JP H07187930A
- Authority
- JP
- Japan
- Prior art keywords
- tert
- butylcalix
- antibacterial agent
- antimicrobial agent
- antibacterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌性製品全般に適用
できる抗菌剤に関する。さらに詳しくは、家庭内におけ
る台所用品、浴室用品、家電製品、病院内における内装
材、シーツ等繊維用品および医療器具に適用可能な抗菌
剤に関する。FIELD OF THE INVENTION The present invention relates to an antibacterial agent applicable to all antibacterial products. More specifically, the present invention relates to an antibacterial agent applicable to kitchen utensils, bathroom products, home appliances, interior materials in hospitals, textile products such as sheets, and medical instruments in the home.
【０００２】[0002]
【従来の技術】抗菌性を有する化合物を樹脂中に含有さ
せ、繊維、塗料を得ることは従来より行われている。抗
菌性を有する化合物のうち、有機系化合物は、毒性が強
く食品や人体に直接接する用途への適用は問題があり、
耐性菌を生じ易い欠点がある。そこで、抗菌性のある銀
などの金属元素を含有した粒子を使用する方法が推奨さ
れている。これらの金属元素含有粒子は、有機系化合物
に比較してその毒性が弱く、耐性菌を生じにくい長所を
有している。2. Description of the Related Art It has been conventionally practiced to incorporate a compound having antibacterial properties into a resin to obtain a fiber or a coating. Among the compounds having antibacterial properties, organic compounds are highly toxic and have problems in application to applications in direct contact with food or the human body.
There is a drawback that resistant bacteria are easily generated. Therefore, a method of using particles containing a metal element such as silver having antibacterial properties is recommended. These metal element-containing particles have the advantages that they are less toxic than organic compounds and less likely to produce resistant bacteria.
【０００３】通常は、粒子の表面積が大きいほうが防菌
に有利なため、ゼオライト、ハイドロキシアパタイトな
どの多孔性セラミックス粒子の表面に金属元素を担持
し、粒子表面に存在する金属元素自体の殺菌作用、もし
くは金属元素が触媒となって発生する活性オゾンによる
殺菌作用を利用している。しかし、粒子表面の金属元素
がイオンとして溶出した場合、これらイオンは紫外線に
より酸化されやすく、例えば銀イオンの場合、太陽光下
程度の紫外線量でも速やかに酸化銀を発生、変色する。Generally, a larger particle surface area is more advantageous for bactericidal prevention, and therefore, a metal element is carried on the surface of porous ceramic particles such as zeolite and hydroxyapatite, and the bactericidal action of the metal element itself present on the particle surface, Alternatively, the bactericidal action of active ozone generated by using a metal element as a catalyst is used. However, when the metal elements on the surface of the particles are eluted as ions, these ions are easily oxidized by ultraviolet rays, and for example, in the case of silver ions, silver oxide is rapidly generated and discolored even with the amount of ultraviolet rays under sunlight.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、毒性
が弱く、着色・変色が少なく、取り扱い易い抗菌剤の提
供にある。An object of the present invention is to provide an antibacterial agent which is less toxic, less colored and discolored, and easy to handle.
【０００５】[0005]
【課題を解決するための手段】すなわち本発明は、フェ
ノ−ル環状縮合体およびまたはその誘導体に、塩基性化
合物の存在下で、抗菌性を有する金属イオンを吸着させ
てなる抗菌剤を提供する。That is, the present invention provides an antibacterial agent obtained by adsorbing a metal ion having an antibacterial property onto a phenol cyclic condensate and / or a derivative thereof in the presence of a basic compound. .
【０００６】フェノ−ル環状縮合体の一つカリックスア
レンは、一般にフェノ−ル誘導体とパラホルムアルデヒ
ドからアルカリ触媒（水酸化カリウムまたは水酸化ナト
リウム）により容易にえられる。フェノ−ル誘導体の種
類とアルカリ触媒の種類および反応温度により、それぞ
れの核体の化合物が得られる。フェノ−ル誘導体として
は、オクチルフェノ−ル、ノニルフェノ−ル、イソ−プ
ロピルフェノ−ル、ｐ-tert-ブチルフェノ−ル、クレゾ
−ル等が挙げられる。特に限定されないが、ｐ-tert-ブ
チルフェノ−ルが合成上好ましい。One of the phenolic cyclic condensates, calixarene, is generally easily obtained from a phenol derivative and paraformaldehyde by an alkali catalyst (potassium hydroxide or sodium hydroxide). Depending on the kind of the phenol derivative, the kind of the alkali catalyst and the reaction temperature, each nucleus compound can be obtained. Examples of the phenol derivative include octylphenol, nonylphenol, iso-propylphenol, p-tert-butylphenol and cresol. Although not particularly limited, p-tert-butylphenol is preferred for synthesis.
【０００７】カリックスアレンはフェノ−ルの環状オリ
ゴマ−で、その核体数により４核体、５核体、６核体、
７核体、８核体に区別される。各核体によりそれぞれ機
能性が異なり、いずれを使用してもすぐれた効果は得ら
れるが、通常は生成、扱い易さから８核体を使用するこ
とが好ましい。Calixarene is a cyclic oligomer of phenol, and depending on the number of nuclides, tetranuclear, pentanuclear, hexanuclear,
It is classified into 7-nucleus and 8-nucleus. The functionality differs depending on each nuclide, and an excellent effect can be obtained regardless of which one is used, but it is usually preferable to use the eight nuclide because it is easy to generate and handle.
【０００８】カリックスアレンおよびその誘導体として
は、ｐ-tert-ブチルカリックス(8)アレン、ｐ-tert-ブ
チルカリックス(7) アレン、ｐ-tert-ブチルカリックス
(6)アレン、ｐ-tert-ブチルカリックス(5) アレン、ｐ-
tert-ブチルカリックス(4)アレン、アセチル化 tert-ブ
チルカリックス(8) アレン、アセチル化 tert-ブチルカ
リックス(7) アレン、アセチル化 tert-ブチルカリック
ス(6) アレン、アセチル化 tert-ブチルカリックス(5)
アレン、アセチル化 tert-ブチルカリックス(4) アレン
等が挙げられる。なお、カッコ内の数字は核体数を示
す。As calixarene and its derivatives, p-tert-butylcalix (8) arene, p-tert-butylcalix (7) arene, p-tert-butylcalix
(6) Allene, p-tert-butylcalix (5) Allene, p-
tert-Butylcalix (4) arenes, acetylated tert-butylcalix (8) arenes, acetylated tert-butylcalix (7) arenes, acetylated tert-butylcalix (6) arenes, acetylated tert-butylcalix (5) )
Allene, acetylated tert-butyl calix (4) arene and the like can be mentioned. The numbers in parentheses indicate the number of nuclear bodies.
【０００９】抗菌性を有する金属イオンの供給源として
は、銀塩、銅塩、亜鉛塩、錫塩、コバルト塩、ニッケル
塩、マンガン塩、鉄塩、アルミニウム塩、例えば硝酸
銀、塩化銀、塩化第二銅、硫酸銅、塩化第一鉄等が挙げ
られる。Sources of antibacterial metal ions include silver salts, copper salts, zinc salts, tin salts, cobalt salts, nickel salts, manganese salts, iron salts, aluminum salts such as silver nitrate, silver chloride, and chloride chloride. Examples include dicopper, copper sulfate, and ferrous chloride.
【００１０】フェノ−ル環状縮合体およびまたはその誘
導体に対し、単に接触させるだけでは抗菌性を有する金
属イオンは吸着されないが、塩基性化合物の存在下で接
触させることにより、金属イオンがフェノ−ル環状縮合
体およびまたはその誘導体に吸着される。塩基性化合物
としては、従来公知のものを用いることができるが、ア
ンモニア並びにメチルアミン、エチルアミン、ジメチル
アミン、ジエチルアミン、トリメチルアミン等のアミン
類が好ましい。Metal ions having antibacterial properties are not adsorbed to the phenol cyclic condensate and / or its derivative by merely contacting it, but when the metal ion is contacted in the presence of a basic compound, the metal ion is converted into phenol. Adsorbed on the cyclic condensate and / or its derivative. As the basic compound, conventionally known compounds can be used, but ammonia and amines such as methylamine, ethylamine, dimethylamine, diethylamine and trimethylamine are preferable.
【００１１】[0011]
【実施例】以下、実施例により本発明を説明する。例
中、部とは重量部を、％は重量％をそれぞれ表す。 〔実施例１〕フラスコ容器に、硝酸銀 0.5部および 10%
アンモニア水91.8部を加え溶解し、ｐ-tert-ブチルカリ
ックス(8) アレン 7.7部を加えた。約 150時間よく攪拌
した後、ろ過洗浄を行い乾燥して抗菌剤を得た。 〔実施例２〕フラスコ容器に、硝酸銀 0.5部、エチルア
ミン 5.0部および水86.8部を加え溶解し、ｐ-tert-ブチ
ルカリックス(6) アレン 7.7部を加えた。約 150時間よ
く攪拌した後、ろ過洗浄を行い乾燥して抗菌剤を得た。EXAMPLES The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. Example 1 A flask container was charged with 0.5 part of silver nitrate and 10%.
91.8 parts of aqueous ammonia was added and dissolved, and 7.7 parts of p-tert-butylcalix (8) arene was added. After stirring well for about 150 hours, it was filtered, washed and dried to obtain an antibacterial agent. Example 2 0.5 part of silver nitrate, 5.0 parts of ethylamine and 86.8 parts of water were added and dissolved in a flask container, and 7.7 parts of p-tert-butylcalix (6) arene was added. After stirring well for about 150 hours, it was filtered, washed and dried to obtain an antibacterial agent.
【００１２】〔実施例３〕フラスコ容器に、硝酸銀 0.5
部、エチレンジアミン 5.0部および水86.8部を加え溶解
し、ｐ-tert-ブチルカリックス(4) アレン 7.7部を加え
た。約 150時間よく攪拌した後、ろ過洗浄を行い乾燥し
て抗菌剤を得た。 〔実施例４〕硝酸銀を塩化銀に代えた以外は、実施例１
と同様にして抗菌剤を得た。 〔実施例５〕硝酸銀を塩化銀に代えた以外は、実施例２
と同様にして抗菌剤を得た。 〔実施例６〕硝酸銀を塩化銀に代えた以外は、実施例３
と同様にして抗菌剤を得た。[Example 3] 0.5 mL of silver nitrate was placed in a flask container.
Parts, 5.0 parts of ethylenediamine and 86.8 parts of water were added and dissolved, and 7.7 parts of p-tert-butylcalix (4) arene was added. After stirring well for about 150 hours, it was filtered, washed and dried to obtain an antibacterial agent. [Example 4] Example 1 except that silver nitrate was used instead of silver nitrate.
An antibacterial agent was obtained in the same manner as. [Example 5] Example 2 except that silver nitrate was used instead of silver nitrate.
An antibacterial agent was obtained in the same manner as. [Example 6] Example 3 except that silver nitrate was used instead of silver nitrate.
An antibacterial agent was obtained in the same manner as.
【００１３】〔実施例７〕ｐ-tert-ブチルカリックス
(6) アレンをｐ-tert-ブチルカリックス(8) アレンに代
え、攪拌時間を24時間にした以外は、実施例２と同様に
して抗菌剤を得た。 〔実施例８〕ｐ-tert-ブチルカリックス(4) アレンをｐ
-tert-ブチルカリックス(8) アレンに代え、攪拌時間を
24時間にした以外は、実施例２と同様にして抗菌剤を得
た。 〔実施例９〕フラスコ容器に、塩化銀 0.5部、エチレン
ジアミン 5.0部および水86.8部を加え溶解し、ｐ-tert-
ブチルカリックス(8) アレン 7.7部を加えた。24時間よ
く攪拌した後、ろ過洗浄を行い乾燥して抗菌剤を得た。Example 7 p-tert-butyl calix
(6) An antibacterial agent was obtained in the same manner as in Example 2 except that p-tert-butylcalix (8) arene was used instead of allene, and the stirring time was 24 hours. [Example 8] p-tert-butylcalix (4) arene was added to p.
-tert-Butyl calix (8)
An antibacterial agent was obtained in the same manner as in Example 2 except that the time was 24 hours. [Example 9] To a flask container, 0.5 part of silver chloride, 5.0 parts of ethylenediamine and 86.8 parts of water were added and dissolved, and p-tert-
Butyl calix (8) allene (7.7 parts) was added. After stirring well for 24 hours, it was filtered, washed and dried to obtain an antibacterial agent.
【００１４】〔比較例１〕フラスコ容器に、硝酸銀 0.5
部および5%アセトン水溶液91.8部を加え溶解し、ｐ-ter
t-ブチルカリックス(8) アレン 7.7部を加えた。24時間
よく攪拌した後、ろ過洗浄を行い乾燥して抗菌剤を得
た。なお、5%アセトン水溶液は、ｐ-tert-ブチルカリッ
クス(8) アレンの濡れをよくするために使用した。[Comparative Example 1] 0.5 mL of silver nitrate was placed in a flask container.
Parts and 51.8% 5% acetone aqueous solution were added and dissolved, and p-ter
7.7 parts of t-butyl calix (8) arene was added. After stirring well for 24 hours, it was filtered, washed and dried to obtain an antibacterial agent. The 5% aqueous acetone solution was used to improve the wetting of p-tert-butylcalix (8) arene.
【００１５】〔比較例２〕ｐ-tert-ブチルカリックス
(8) アレンをｐ-tert-ブチルカリックス(6) アレンに代
えた以外は、比較例１と同様にして抗菌剤を得た。 〔比較例３〕ｐ-tert-ブチルカリックス(8) アレンをｐ
-tert-ブチルカリックス(4) アレンに代えた以外は、比
較例１と同様にして抗菌剤を得た。Comparative Example 2 p-tert-butyl calix
(8) An antibacterial agent was obtained in the same manner as in Comparative Example 1 except that p-tert-butylcalix (6) arene was used instead of allene. [Comparative Example 3] p-tert-butylcalix (8) arene was added to p.
An antibacterial agent was obtained in the same manner as in Comparative Example 1 except that -tert-butylcalix (4) arene was used instead.
【００１６】実施例１〜９および比較例１〜３で得られ
た試験品２部に、ライオポ−ル (東洋インキ製床用塗料
「ライオポ−ルIX-226G-215 トップ A」／「ライオポ−
ルIX-226 シリ−ズ B」=2/1、固形分60%)98部を混合
し、枠型に流し込み硬化させ、厚さ１mmの試験資料とし
た。To 2 parts of the test products obtained in Examples 1 to 9 and Comparative Examples 1 to 3, was added lyopol (Toyo Ink floor paint "Liopol IX-226G-215 Top A" / "Liopol".
98 parts of IX-226 series B ”= 2/1, solid content 60%) were mixed, poured into a frame mold and cured, and used as a test material having a thickness of 1 mm.
【００１７】（抗菌性試験）表１に示す菌を５×５cm2
の試験資料表面に噴霧し、24時間培養した。培養後、検
体を含まない対照の増殖程度と比較し抗菌活性を評価し
た。抗菌活性は、菌の増殖程度が対照の増殖レベルと同
等の場合を−、対照の増殖レベルの50％程度までの場合
を＋、ほぼ完全に抑制された場合を＋＋とした。結果を
表１に示す。(Antibacterial test) The bacteria shown in Table 1 were 5 × 5 cm 2
The test material surface was sprayed and cultured for 24 hours. After culturing, the antibacterial activity was evaluated by comparing with the growth degree of a control containing no sample. The antibacterial activity was defined as-when the growth level of the bacteria was equivalent to the growth level of the control, + when up to about 50% of the growth level of the control, and ++ when it was almost completely suppressed. The results are shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】（耐候性試験)試験資料を「キセノンロン
グライフウェザオメ−タ−」にて、湿度70% 下で72時
間、 168時間、 480時間の耐候性試験を行った。冷暗所
に保存した資料を対照資料とし、変色度合いを目視で評
価した。評価基準は、変色なしを５、変色顕著を１と
し、５段階で表した。結果を表２に示す。(Weather resistance test) A test material was subjected to a weather resistance test with "Xenon Long Life Weatherometer" at a humidity of 70% for 72 hours, 168 hours, and 480 hours. A material stored in a cool and dark place was used as a reference material, and the degree of discoloration was visually evaluated. The evaluation standard was expressed in 5 stages, with 5 indicating no discoloration and 1 indicating remarkable discoloration. The results are shown in Table 2.
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【発明の効果】本発明により、耐熱性が優れ、着変色が
少なく、取扱い易く、広範囲に利用でき、工業的に極め
て有用な抗菌剤が提供できるようになった。Industrial Applicability According to the present invention, it is possible to provide an antibacterial agent which is excellent in heat resistance, has little discoloration due to discoloration, is easy to handle, can be used in a wide range, and is extremely useful industrially.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ０１Ｎ 59/16 Ｚ 59/20 Ｚ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area A01N 59/16 Z 59/20 Z
Claims (2)
導体に、塩基性化合物の存在下で、抗菌性を有する金属
イオンを吸着させてなる抗菌剤。1. An antibacterial agent obtained by adsorbing a metal ion having an antibacterial property onto a phenol cyclic condensate and / or its derivative in the presence of a basic compound.
鉛、錫、コバルト、ニッケル、マンガン、鉄およびアル
ミニウムから選ばれる少なくとも一種であることを特徴
とする請求項１記載の抗菌剤。2. The antibacterial agent according to claim 1, wherein the metal ion having antibacterial property is at least one selected from silver, copper, zinc, tin, cobalt, nickel, manganese, iron and aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05327245A JP3077486B2 (en) | 1993-12-24 | 1993-12-24 | Antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05327245A JP3077486B2 (en) | 1993-12-24 | 1993-12-24 | Antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07187930A true JPH07187930A (en) | 1995-07-25 |
| JP3077486B2 JP3077486B2 (en) | 2000-08-14 |
Family
ID=18196955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05327245A Expired - Lifetime JP3077486B2 (en) | 1993-12-24 | 1993-12-24 | Antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3077486B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0954965A1 (en) * | 1998-05-05 | 1999-11-10 | Rohm And Haas Company | Controlled release compositions |
| CN1086109C (en) * | 1999-08-12 | 2002-06-12 | 中国建筑材料科学研究院 | Air-purifying and antibiotic functional material activated by rare-earth to generate anions, and production method thereof |
| CN115246956A (en) * | 2021-04-26 | 2022-10-28 | 合肥杰事杰新材料股份有限公司 | Modified AgO antibacterial agent, preparation method thereof and antibacterial material |
-
1993
- 1993-12-24 JP JP05327245A patent/JP3077486B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0954965A1 (en) * | 1998-05-05 | 1999-11-10 | Rohm And Haas Company | Controlled release compositions |
| CN1086109C (en) * | 1999-08-12 | 2002-06-12 | 中国建筑材料科学研究院 | Air-purifying and antibiotic functional material activated by rare-earth to generate anions, and production method thereof |
| CN115246956A (en) * | 2021-04-26 | 2022-10-28 | 合肥杰事杰新材料股份有限公司 | Modified AgO antibacterial agent, preparation method thereof and antibacterial material |
| CN115246956B (en) * | 2021-04-26 | 2024-04-09 | 合肥杰事杰新材料股份有限公司 | Modified AgO antibacterial agent, preparation method thereof and antibacterial material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3077486B2 (en) | 2000-08-14 |
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